WO2003064538A1

WO2003064538A1 - Purified purple corn color and method of preparing the same

Info

Publication number: WO2003064538A1
Application number: PCT/JP2002/000822
Authority: WO
Inventors: Takahito Ichi; Makoto Sakata; Hiromitsu Aoki; Takatoshi Koda
Original assignee: San-Ei Gen F.F.I., Inc.
Priority date: 2002-02-01
Filing date: 2002-02-01
Publication date: 2003-08-07
Also published as: JPWO2003064538A1; EP1477530A1; JP4134906B2; US20050125915A1; CA2474881C; EP1477530A4; US7192456B2; CA2474881A1; EP1477530B1

Abstract

Purple corn color which has a high safety and no odor originating in aroma components since impurities (aroma components, precursor thereof, a fungal toxin fumonicin, etc.) seemingly contained in the purple corn material have been eliminated therefrom; and color preparations containing the same. This purple corn color can be obtained by a preparation method comprising passing a purple corn color extract through an adsorptive resin, washing with water, and releasing the purple corn color from the resin with the use of a 25 to 45 v/v % aqueous solution of an alcohol.

Description

Specification

Purified purple corn pigment and method for preparing the same

TECHNICAL FIELD The present invention relates to an odorless or slightly odorless purple corn dye having no or significantly reduced odor and a dye preparation containing the dye. In addition, the present invention relates to an odorless or slightly odorous purple corn pigment, which can be caused by the influence of light or heat during storage and which has a significantly suppressed odor over time, and a pigment preparation containing the pigment. Furthermore, the present invention relates to an odorless or slightly odorless purple corn pigment containing no fumonisin and a pigment preparation containing the pigment.

Further, the present invention provides a method for purifying a purple corn pigment capable of significantly removing fumonisin which may be contained in a purple corn pigment extract, in other words, a method for preparing an odorless or slightly odorless purified purple corn pigment containing no fumonisin. About.

Background art

Purple corn pigment, which is an anthocyanin pigment, is a pigment widely used mainly for coloring foods such as beverages. However, since the purple corn mouth pigment has a peculiar aroma component and impurities derived from the raw material of purple corn, when used in foods and other products, the aroma and sediment generated from the aroma component and impurities are used. May have an adverse effect on the flavor and taste of these foods. For this reason, there has been a demand for a pigment preparation containing a purple corn pigment from which fragrance components and impurities peculiar to purple corn have been significantly removed, and various purification methods have been studied.

However, there has been almost no method for effectively deodorizing the odor peculiar to purple corn pigment, and the conventional purple corn pigment preparation still has a peculiar aroma derived from purple corn. In addition, conventional purple corn pigment preparations have a problem that the odor gradually increases due to changes over time due to heat, light, or the like during long-term storage, and a so-called “smell return phenomenon” occurs. It is a fact.

Furthermore, since purple corn pigment and its pigment preparation are widely used as food coloring agents, they must be prepared so that fumonisin, which is a mold venom that can be generated in purple corn as a raw material, is not mixed. Desired. DISCLOSURE OF THE INVENTION Based on these facts, the present invention provides a purple corn that can be safely used as a coloring agent without affecting the flavor and flavor of foods, pharmaceuticals, quasi-drugs, cosmetics, etc. It is intended to provide a dye.

Specifically, the present invention firstly provides a purple corn pigment and a pigment obtained by removing an aroma component contained in the purple corn and eliminating an odor derived from the aroma component or by significantly reducing the odor. It is intended to provide a pigment preparation containing the same. Secondly, an object of the present invention is to provide a purple corn pigment which does not change with time such as so-called "smell reversion" due to heat or light during long-term storage, and a pigment preparation containing the pigment. . Thirdly, the present invention relates to a purple corn pigment which has significantly reduced aroma components and contaminants and further does not contain or significantly reduces fumonisin, which is a capi venom, and a pigment preparation containing the pigment. It is intended to provide. A fourth object of the present invention is to provide a method for preparing the purified purple corn pigment, particularly a method for preparing a purple corn pigment that can be effectively used for removing fumonisin generated in purple corn as a raw material. .

The present inventors have conducted diligent studies day and night to solve the conventional problems relating to the above-mentioned purple corn pigment preparation, and selectively removed impurities and fumonisins that cause odor from the purple corn pigment extract. The present inventors have found a method for obtaining a pigment, and have developed a purified purple corn pigment and a pigment preparation thereof that meet the above-mentioned objectives.

That is, the present invention is a method for preparing a purple corn pigment described in the following (1) to (10): (1) Pass the purple corn pigment extract through the adsorbent resin, wash the resin with the adsorbed pigment with water, and then use a 25-45 v / v% alcohol aqueous solution as the desorbent to remove the purple corn pigment from the resin. A method for preparing a purple corn pigment, comprising a step of removing the pigment.

(2) The method for preparing a purple corn pigment according to (1), wherein the purple corn pigment extract is acidic water or an acidic aqueous solution containing 2 Ov / v% or less of alcohol.

(3) After washing with water, a desorbing liquid 1.5 to 2.5 times the resin volume is passed through the resin at a velocity of SV (space velocity) = 0.8 to 1.5 (1) or (2) 3. The method for preparing a purple corn pigment according to the above.

(4) The method for preparing a purple corn dye according to any one of (1) to (3), wherein the adsorption resin is a crosslinked styrene-based porous polymer.

(5) A step of passing the purple corn pigment extract through the adsorption resin, washing with water, and then removing the purple corn pigment from the resin using a 25 to 45 v / v% alcohol aqueous solution as a desorbing liquid. The method for preparing a purple corn pigment according to any one of (1) to (4), wherein the method comprises a step of removing fumonisin.

(6) Select from the group consisting of adsorption treatment, ion exchange treatment, acid treatment, extraction treatment and membrane separation treatment for the adsorption treatment liquid obtained in the step described in any of (1) to (5). A method for preparing a purple corn pigment, wherein the method comprises performing at least one kind of treatment.

(7) The method for preparing a purple corn dye according to (6), wherein a membrane separation treatment is performed after the treatment step described in any of (1) to (5).

(8) The method for producing a purple corn dye according to (6) or (7), wherein the membrane separation treatment is at least one of a reverse osmosis membrane treatment and an ultrafiltration membrane treatment.

(9) The method for preparing a purple corn dye according to (7), wherein an acid treatment is performed before the membrane separation treatment. No

(10) The method for preparing a purple corn pigment according to (9), wherein the acid treatment is performed under a high temperature condition. In addition, the above-mentioned methods (1) to (6) for preparing a purple corn pigment can be rephrased as a method for removing fumonisin from a purple corn pigment extract. Further, the method for preparing a purple corn pigment described in the above (1) to (10) can be rephrased as a method for purifying a purple corn pigment.

Further, the present invention is a purple corn pigment listed in the following (11) to (14):

(11) A purple corn pigment which does not contain fumonisin, which is prepared by the method according to any one of (1) to (10).

(12) A purple corn pigment prepared by the method according to any one of (1) to ο), which has a color value of

E ^10% _lcm = 60

A purple corn pigment with a total odor component concentration of 150 ppm or less.

(13) The fragrance component in the purple corn pigment is at least one selected from the group consisting of acetic acid, gerethyl ester malonate, 4-vinyl-2-methoxyphenol and 4-vinylphenol. The described purple corn pigment.

(14) A purple corn pigment prepared by the method according to any one of (1) to (10), which has a color value of

E ^10% _lcm = 60

A purple corn pigment having a total concentration of acetic acid, malonic acid getyl ester, 4-vier-2-methoxyphenol and Z or 4-bierphenol which is less than or equal to 20 ppm.

Furthermore, the present invention is a pigment preparation containing the purple corn pigment according to any one of the above (11) to (14).

BRIEF DESCRIPTION OF THE FIGURES

Figure 1 shows the amount of aroma components contained in the purple corn pigment preparation of Example 1 (Figure A) and the purple corn pigment preparation of Comparative Example 1 (Figure B) by gas chromatography and mass spectrometry (GC-MS FIG. 7 shows the result of the measurement in FIG. The figure In 1, the peak of (1) indicates acetic acid, the peak of (2) indicates getyl malonate, the peak of (3) indicates 4-bier-2-methoxyphenol, and the peak of (4) indicates 4-bierphenol. The peak of IS-1 is methyl octanoate, which is an internal standard.

FIG. 2 is a diagram showing the results of analysis of fumonisin by HPLC of the purple corn pigment preparation of Comparative Example 2 (FIG. A) and the purple corn pigment preparation of Example 2 (FIG. B) treated by the production method according to the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention provides a purple corn color which does not contain or is significantly reduced in flavor components and impurities derived from purple corn used as a raw material.In the present invention, purple corn pigment is mainly used for beverages, confectionery and the like. Is an anthocyanin pigment widely used for coloring foods, and is prepared from purple corn (Zea mays L .: Poaceae).

In the present invention, the color value refers to the absorbance at a maximum absorption wavelength (around 510 nm) in the visible part of a solution (buffer solution PH3.0) containing the target purple corn dye, and the absorbance is measured at 10 watts. It is a numerical value converted to the absorbance of the / v% solution. Further, in the present invention, the fragrance component means a volatile fragrance component derived from purple corn which causes an unpleasant odor or an unpleasant odor, and is not particularly limited. Specifically, acetic acid, getyl malonate, 4 -Biel-2-methoxyphenol, and 4-vinylphenol. In addition, examples of the contaminants include poorly water-soluble pigment components, waxes, residual pesticides, molds and their products (for example, fumonisin) which are lately generated in crops.

Fumonisins include fumonisins A1, fumonisins A2, fumonisins Bl, fumonisins B2, fumonisins B3, etc., and these include molds that occur in corn and other cereals. F.

ro ifara b), which is reported to have toxicity such as hepatocarcinogenesis.

The purple corn pigment targeted by the present invention has a color value of the pigment. E ^10% _lcm = 60

Wherein the total concentration of the aroma components contained in the pigment is 150 ppm or less. The concentration of the aroma component is almost proportional to the color value. Therefore, the purple corn pigment targeted by the present invention may be any one as long as the total concentration of the aroma components contained in the pigment is within the above-mentioned concentration range when the pigment is adjusted to the above-mentioned color value. Need not have the above color values.

Preferably, as the purple corn pigment of the present invention, when the color value of the pigment is adjusted as described above, acetic acid, getyl ester malonate, 4-pinyl-2-methoxyphenol and / or 4 -The concentration of pierfenol is about 50 ppm or less in total, more preferably about 20 ppm or less. These components are volatile odor components derived from purple corn that cause malodor.

The purple corn pigment of the present invention, which is deodorized or has a reduced odor, due to the extremely reduced content of the above-mentioned aroma components, is subjected to an adsorption treatment and an ion exchange with the purple corn pigment extract. It can be manufactured and obtained by performing any one of processing, pH adjustment processing, extraction processing, and membrane separation processing, or by arbitrarily combining two or more of these processing. An acid treatment can be suitably used as the pH adjustment treatment.

As the pigment extract of purple corn used in the present invention, a solvent extract of a purple corn plant is used. The plant part used for the extraction may be any part containing the target purple corn pigment, and it does not matter whether the whole plant or a part thereof (for example, female spikelets (fruit, core), etc.) is used. . The above-mentioned plant also includes calli of a purple corn plant. The whole plant or a part thereof of the plant may be subjected to the extraction operation as it is (raw) or as a crushed product, or after drying, may be subjected to the extraction operation as a pulverized powder if necessary. You may.

As the solvent used for the above extraction, a pigment contained in purple corn is used. The solvent is not particularly limited as long as it can be extracted, but alcohol, water, or a mixture thereof can be preferably used. Examples of the alcohol include lower alcohols having 1 to 4 carbon atoms such as methanol, ethanol, propanol, isopropyl alcohol, and butanol. Preferably, it is an acidic water or an acidic alcohol aqueous solution. The acidic water or acidic alcohol aqueous solution can be prepared by using an inorganic acid such as hydrochloric acid, sulfuric acid or phosphoric acid or an organic acid such as citric acid or malic acid, to pt ^ 3 l-5, preferably pH about 1-4. Is preferably adjusted to the range described above. The amount of alcohol contained in the aqueous alcohol solution is preferably 20% by volume or less.

As the extraction method, a generally used method can be adopted. Although there is no limitation, for example, a method of immersing whole plants or parts (as is or coarse, finely chopped) or their dried and crushed materials (such as powder) in a solvent by cold immersion, digestion, etc. Extraction is carried out while heating and stirring, followed by filtration to obtain an extract, or bar collation.

The obtained extract is subjected to filtration treatment, coprecipitation, or centrifugation as necessary, and then subjected to adsorption treatment as it is or after being concentrated. The adsorption treatment can be performed according to a conventional method, and examples thereof include an adsorption treatment using activated carbon, silica gel, or a porous ceramic, and an adsorption treatment using various synthetic adsorption resins. The synthetic adsorption resin is not particularly limited, but preferably includes a crosslinked styrene-based or acrylic-based porous polymer. Specifically, a cross-linked styrene-based porous polymer includes a styrene-vinylbenzene copolymer, and commercially available products such as Diaion HP10, Diaion HP20, Diaion HP21, Diaion HP40, and Diaion HP50; Sepabeads SP70, Sepabeads SP700, Sepabeads SP825 (trademark, manufactured by Mitsubishi Chemical Corporation); Amberlite XAD-4; Duolite S874, Duolite S876 (trademark, manufactured by Rohm & Haas) Is exemplified. Examples of the acrylic porous polymer include Amberlite XAD-7, Amberlite XAD-8, and Amplifylite XAD-2000; Duolite S877 (trademark, manufactured by Rohm & Haas). use The synthetic adsorption resin to be used is preferably a crosslinked styrene-based porous polymer, more preferably a styrene-vinylbenzene copolymer, and even more preferably a diamond HP-based adsorption resin.

The adsorption resin is not limited, but preferably has a specific surface area of about 600 m ² / g and a pore radius of 100 to 40θΑ, preferably 200 to 30θΑ.

Next, the resin adsorbed with the purple corn pigment extract is washed and then subjected to a desorption treatment. Washing is usually carried out with water, and is preferably carried out by passing 2 to 5 times, preferably 3 to 4 times, the volume of the resin. The dye can be removed by passing an aqueous alcohol solution through the adsorption resin. At this time, an alcohol aqueous solution is preferably used at a ratio of 25 to 45 v / v%, preferably 28 to 40 v / v%, more preferably 28 to 35 v / v% as an aqueous alcohol solution. An aqueous alcohol solution is used. By using a desorbing solution having such an alcohol concentration, the purple corn pigment is selectively removed from the resin with high yield while fumonisin, which may be contained in the purple corn pigment extract, is adsorbed to the resin. Separated and can be collected. In this case, it is preferable that the amount of the desorbed liquid is usually 1 to 3 times, preferably 1.5 to 2.5 times the volume of the resin.

Although not particularly limited, the adsorption resin treatment is usually performed at room temperature. In addition, the flow rate of the purple corn pigment extract, washing solution and desorbing solution is usually set to SV (space velocity) = 0.1 to 5, preferably SV = 0.5 to 3, more preferably 0.8 to L.5. Can be.

Thus, fumonisin is significantly removed, and an adsorption-treated solution of a pigment extract of purple corn sorghum that does not contain fumonisin can be obtained.

The adsorption treatment solution of the purple corn pigment extract thus obtained is subjected again to adsorption treatment as necessary, or ion exchange treatment, membrane separation treatment, extraction treatment, pH adjustment treatment (acid treatment), etc. For various treatments. The adsorption treatment is not limited to the treatment described above, and can be carried out using various kinds of adsorption resins according to a conventional method. The ion exchange treatment is not particularly limited, and a cation exchange treatment or an anion exchange treatment can be performed using a conventional resin according to a conventional method. For example, the cation exchange resin is not limited, but may be Diaion SK 1B, Diaion SK 102, Diaion SK 116, Diaion PK 208, Diaion WK10, Diaion WK20 (trademark, manufactured by Mitsubishi Chemical Corporation). , Etc., and as the anion exchange resin, although not limited, Diaion SA 10A, Diaion SA 12A, Diaion SA 20A, Diaion PA 306, Diaion WA 10, and Diaion WA 20 (trademark) And Mitsubishi Chemical Corporation).

The term “membrane separation method” as used in the present invention broadly means a filtration method using a membrane. For example, functions such as a membrane filter (MF) membrane, an ultrafiltration (UF) membrane, a reverse osmosis membrane, and an electrodialysis membrane are used. Filtration treatment using a conductive polymer membrane. Examples of the membrane separation method include ultrafiltration membrane method and reverse osmosis membrane method using these membranes, dialysis method using concentration gradient by ion separation membrane, and application of voltage using ion exchange membrane as diaphragm. An electrodialysis method is known. Industrially, a membrane separation method by a reverse osmosis membrane method is preferable. Regarding the membrane material used in such a membrane separation method, regardless of whether it is natural, synthetic, or semi-synthetic, for example, cellulose, cell di-acetate or tri-acetate, polyamide, polysulfone, polystyrene, polyimide, Polyacrylonitrile and the like can be mentioned.

The membrane separation process of the present invention, molecular weight cutoff of, for example, 10 ⁴ ~: L0 processing method and fractional molecular weight to separate off the polymeric compound using a certain film in the range of ⁶ approximately 2000 to 4000, preferably Includes a treatment method for separating and removing low molecular compounds using about 3000 membranes. As the former method, specifically, ΝΤϋ-3150 film, NTU-3250 film, NTU-3550 film, NTU-3800 film (Nitto Denko); Cefilt-UF (Nippon NGK); , Tang-3013 membrane, AHP-1010 membrane (from Asahi Kasei); etc., and the ultrafiltration (UF) membrane treatment can be mentioned. As the latter method, specifically, NTR-7250 membrane, NTR-7410 film, NTR-7430 film, NTR-7450 film (Nitto Denki), AIP-3013 film, ACP-3013 film, ACP-2013 film, AIP-2013 film, AI0-1010 film Reverse osmosis membranes (nanofiltration membranes, molecular weight cutoff of about 3000) using membranes such as those manufactured by Asahi Kasei. These may be performed alone or in combination of two.

In the present invention, the extraction treatment is not particularly limited, but carbon dioxide, ethylene, propane, etc. are brought into contact with the adsorption treatment liquid of the purple corn pigment extract in a closed system at a temperature and pressure above the critical point. Methods can be mentioned. The pH adjustment treatment (acid treatment) is carried out by adjusting the pH of the purple corn pigment extract adsorption treatment solution or the treatment solution subjected to the various treatments described above to pH 1 to 4 and exposing it to acidic conditions. Can be implemented. Preferably, the acid treatment is performed under the conditions of PHI. Specifically, the acid treatment can be easily performed by adding an acid to the treatment liquid. The acid is not particularly limited as long as it is an acid commonly used as a food additive, and can be arbitrarily selected from such acids. Examples thereof include organic acids such as citric acid, acetic acid, malic acid, and lactic acid, and inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, and nitric acid. Acid treatment using an inorganic acid usually used as a food additive is preferred.

The temperature conditions for performing such acid treatment are not particularly limited, and can be appropriately selected and used usually in the range of 5 to 100 ° C. The acid treatment time is not particularly limited, and can be appropriately selected usually in the range of 1 to 300 minutes. The acid treatment is preferably carried out under high temperature conditions, and such a temperature may be in the range of 40 to LOOT, preferably 50 to 80 ° C. In this case, the acid treatment time can be appropriately selected from the range of 1 to 60 minutes, preferably 10 to 30 minutes. In the acid treatment step, the treatment liquid is not particularly limited with or without stirring.

The above-mentioned various treatments may be performed alone on the adsorption treatment liquid of the purple corn pigment extract, or may be performed by combining any two or more treatments in any order. It may be repeated under the same or different conditions.

Although a preferred treatment method is not particularly limited, a method in which an adsorption treatment is performed on the purple corn dye extract, and a membrane separation treatment is performed after the desorption treatment step. You. More preferably, the acid treatment is performed after the adsorption treatment step, and the membrane separation treatment is performed after the acid treatment. Note that such acid treatment is preferably performed under high temperature conditions. If necessary, an ion exchange treatment (preferably, an anion exchange resin treatment) can be performed after the desorption treatment.

Here, the membrane separation treatment is preferably a reverse osmosis membrane treatment or an ultrafiltration membrane treatment, and more preferably a reverse osmosis membrane treatment. Further, the membrane separation treatment is preferably performed using a membrane having a molecular weight cut-off of 2,000 to 4,000, preferably around 3,000.

In general, grasses such as maize are easily contaminated by fumonisin, a mold venom component. The purple corn used as a raw material of the pigment of the present invention is also a kind of corn and may be contaminated with fumonisin. According to the method of the present invention described above, even if purple corn used as a raw material is contaminated with fumonisin, it is possible to effectively remove fumonisin from the purple corn pigment, thus containing fumonisin. No safe purple corn pigment can be provided. Here, “does not include” means that the concentration of fumonisin contained in the dye or the dye preparation is below the detection limit of 0.2 ppm.

Further, the purple corn pigment of the present invention obtained by the above method, in addition to various contaminants including fumonisin, the above-mentioned fragrance component derived from purple corn is effectively removed, and Accordingly, it is possible to provide a slightly odorless purple corn pigment whose odor is reduced to such an extent that it has no odor or its flavor is hardly affected even when incorporated in food. Further, the purple corn pigment of the present invention obtained by the above method does not cause a change over time such as so-called “smell return” even under the influence of heat or light during long-term storage. This is presumably because the production method of the present invention decomposed or removed the precursor of the fragrance component contained in the contaminants, which could cause off-flavor and odor.

The purple corn pigment of the present invention thus obtained is in the form of a solution dissolved or dispersed in water, alcohol (for example, ethanol), or other solvents. Alternatively, it can be prepared as a pigment preparation in a dry state (powder, granule, tablet, pill, etc.).

Therefore, the present invention provides a pigment preparation containing a purple corn pigment that can be safely used as a coloring agent for foods, pharmaceuticals, quasi-drugs, cosmetics, and the like. The pigment preparation may contain a food hygiene or pharmaceutically acceptable carrier or additive in addition to the purple corn pigment of the present invention. Specifically, as such a carrier and additive, for example, In addition to dextrin, lactose and powdered starch syrup, food additives and pharmaceutical additives such as preservatives, stabilizers or antioxidants usually used for pigments and pigment preparations can be mentioned. Example

Hereinafter, examples and comparative examples will be described in order to further clarify the configuration and effects of the present invention. However, the present invention is not affected at all by these examples.

Reference Example Preparation of Purple Corn Pigment Extract

2 kg of dried purple corn (cotyledon (core and grain)) is added to a mixture of 16 L of water, 4 L of ethanol and 90 g of sulfuric acid (pH 2.3), and left overnight at room temperature to remove red pigment. Extracted. After the extraction, a filter aid and diatomaceous earth were added to the liquid that had been subjected to solid-liquid separation using a 60-mesh wire mesh, and the mixture was filtered through filter paper to obtain about 16 L of a purple corn pigment extract.

Experimental example 1

To about 16 L of the purple corn pigment extract prepared according to the method of Reference Example, a standard product of fumonisin B1 was added to a concentration of 5 ppm. Next, 16 L of this fumonisin-containing extract was passed through 1.5 L of an adsorption resin (styrene vinyl benzene copolymer: Dyaryon HP20, manufactured by Mitsubishi Chemical Corporation) under the conditions of SV = 1 and a temperature of 20. Was washed with 5 L of water (SV = 1). Next, 3 L of a 30 v / v% aqueous ethanol solution was passed through the obtained resin (SV = 1, temperature: 20 ° C.), and the desorbed liquid was recovered (the product of the present invention). On the other hand, as a comparative experiment, the above resin desorption treatment was performed using a 50 v / v% ethanol aqueous solution instead of a 30 v / v% ethanol aqueous solution. The eluate was collected (comparative product). Both desorbed solutions were concentrated under reduced pressure to obtain 800 g of a dye solution having a color value of E 1 ^Q% 1 cm = 100 for each. To 800 g of these dye solutions were added 227 g of water, 40 g of citric acid (crystals) and 266 g of ethyl alcohol to prepare 1333 g of a purple corn dye preparation having a color value E of ^10% lcm = 60.

Next, the content of mold venom (fumonisin) in the purple corn pigment preparations (invention product, comparative product) prepared above was determined by liquid chromatography.

(HPLC) was used for quantitative analysis. Specifically, each pigment preparation (color value E ^{1 ()%} _lcm = 60) lg is diluted with 50 ml of a mixture of methanol: water = 3: 1 and adjusted to pH 7.0 with 1N sodium hydroxide. Filter with 0.5 0.51 membrane. The filtrate is allowed to flow naturally to a Bond Elut SAX (Varian CA 90710) column, which is a solid phase extraction cartridge, to adsorb fumonisin. After washing with 10 ml of a mixture of methanol: water = 3: 1 and 5 ml of methanol, 1 ° /. Elute fumonisin with 30-40 ml of methanol containing acetic acid. The fumonisin eluate was evaporated to dryness under reduced pressure and dissolved in 0.1 M borate buffer (pH 8.7) 200 / L to obtain a test sample for analysis. It was measured.

Column: L-columnODS (4.6mm X 250mm, manufactured by Chemical Inspection Association) Column temperature: 35

Mobile phase: Methanol containing 0.05% trifluoroacetic acid: water = 3: 2 mixture Mobile phase flow rate: l.Oml / min

Reaction tube: ID 0.25mm X 5000mm (SUS) Load after passing through the column and before detection

Reaction tube temperature: 50 ° C

Reaction solution: 0.08% 0-phthalaldehyde, 0.1N-acetyl-L-cysteine 0.4M boric acid buffer ρΗΙΟ.Ο solution, injected before reaction tube after passing through column

Reaction solution flow rate: 0.4ml / min

Detection wavelength: fluorescence excitation wavelength 340mn, fluorescence measurement wavelength 450nm.

As a result, a purple solution prepared using a 50 v / v% ethanol aqueous solution The concentration of fumonisin in the corn pigment preparation was 3 ppm, whereas the concentration of fumonisin in the purple corn pigment preparation prepared using a 30 v / v% aqueous ethanol solution as the eluent was Oppm, and the method of the present invention was used. As a result, it was confirmed that fumonisin was significantly removed.

Experimental example 2

(1) Preparation of purple corn pigment preparation

(1) Approximately 16 L of purple corn pigment extract prepared according to the method of Reference Example was passed through a synthetic adsorption resin Amberlite XAD-7 (1.5 L, acrylate resin, manufactured by Rohm & Haas) for adsorption treatment. After thoroughly washing the resin with 5 L of water, fractionation treatment was performed using a 0% and 50% by volume aqueous ethanol solution as a desorbing solution, and a red fraction was visually obtained (flow-through liquid). Speed: SV = 1, room temperature). As a result, 4.8 L of a purple corn pigment eluate was obtained from the 30-40% by volume ethanol aqueous solution fraction.

Then, the eluate is treated at 3 kg / cm ² at 20 ° C using an ultrafiltration membrane (AHP-2013 membrane: manufactured by Asahi Kasei Corporation, molecular weight cut off: 50,000), and the ultrafiltration permeate is treated. I got Next, sulfuric acid is added to the obtained ultrafiltration permeate to adjust the pH to 2.0, and 5 L of water is further added to reverse osmosis membrane treatment (NTR-725G membrane: manufactured by Nitto Denko; 2,000) to obtain 1 L of reverse osmosis membrane treatment solution. At this time, the contaminants were permeated and removed as a filtrate, and the purified dye component was concentrated as a residual solution. Then, the reverse osmosis treatment solution was concentrated under reduced pressure to obtain 80 g of a significantly purified dye solution having a color value of E ^{1 G%} i _C m = 200. This pigment solution contained 3.1% by weight of cyanidin 3-0-j8-D-glucoside, which is a main pigment component of purple corn pigment. To 80 g of this dye solution, 130 g of water, 40 g of ethyl alcohol and 10 g of citric acid (crystal) were added to prepare 260 g of a purple corn dye preparation having a color value of E ^{1 Q%} _{1 C} m = 60 (the present invention product). ). The pigment preparation was odorless.

② On the other hand, for comparison, about 16 L of purple corn pigment extract prepared according to the method of Reference Example was adsorbed on the synthetic adsorption resin Amberlite XAD-7 (1.5 L) in the same manner as above, and 5 L of water was used. After thoroughly washing the resin, the purple corn dye was eluted with a 50% by volume aqueous ethanol solution to obtain 5 L of eluate. Then this elution The solution was concentrated under reduced pressure to obtain 800 g of a dye solution having a color value of E ^{1 Q%} icm = 100. 223 g of water, 30 g of citric acid (crystal) and 267 g of ethyl alcohol were added to 800 g of this dye solution to prepare 1330 g of a purple corn dye preparation having a color value of E ^{1 Q%} _lcm = 60.

(Comparative product). The pigment preparation had a peculiar off-odor derived from purple corn.

(2) GC-MS measurement

The amount of aroma components contained in each of the purple corn pigment preparations (the present invention product and the comparative product) prepared in (1) above was compared using a gas chromatography / mass spectrometer (GC-MS). Specifically, 30 g of each pigment preparation (E ^{1 D%} i _cm = 60) was collected and extracted with 200 ml of methyl ether containing 0.5 ppm of methyl octanoate as an internal standard substance. Is evaporated to dryness, and the obtained concentrate is subjected to gas chromatography / mass spectrometry under the following conditions.

(GC-MS) to measure the amount of aroma components.

<GC-MS measurement conditions>

GC / MS: Hewlett-Packard 5973, Mass Selective Detector, Column: J-W DB-WAX (0.25 thigh x 60m),

Temperature conditions: Inlet 250 ° (:, interface 230,

Column temperature 5 (TC (2 minutes)-220, temperature rise 3 ° C / min, split ratio: 70: 1,

Ionization voltage: 70 eV.

The results are shown in Figure 1. As shown by A in FIG. 1, according to the total ion chromatogram of the purple corn pigment preparation of the present invention (product of the present invention), the odor components (acetic acid, geryl malonate, 4-vier- Total amounts of 2-methoxyphenol and 4-biphenol) were extremely small (lllppm or less). On the other hand, as shown in Fig. 1B, the comparative purple corn pigment preparation contains a large amount of many volatile components (total amount).

215 ppm) was observed. This result was consistent with the above fact that the product of the present invention was odorless, while the comparative product had a peculiar off-odor derived from purple corn. In Fig. 1, peak (1) indicates acetic acid, peak (2) indicates getyl ester malonate, peak (3) indicates 4-vinyl-2-methoxyphenol, and peak (4) indicates 4-biphenol. The peak of IS-1 is methyl octanoate, which is an internal standard.

(3) Flavor evaluation and storage test

Regarding the purple corn pigment preparation (product of the present invention and comparative product) produced in (1) above, the flavor immediately after production and the flavor after storage at 5, 25 ° C or 38 ° C for 15 to 30 days, respectively. Was evaluated by a panel of 10 well-trained flavorists. In addition, a beverage type solution (color value E ^10% icm 0.04, Brix. ¹⁰ °, 0.2% aqueous solution of citric acid, no flavor added) was prepared using each pigment preparation, and the solution was also the same as above. The flavors immediately after preparation and after storage were compared and evaluated. Table 1 shows the results.

A: No odor at all B: Slight odor

C: Off-flavor D: Off-flavor

E: has a very strong odor As can be seen from the results immediately after production shown in Table 1, the product of the present invention had a significantly reduced odor compared to the comparative product, and was determined to be an odorless dye. In addition, the comparative product becomes more and more fragrant as the storage time is increased to 15 to 30 days, while the product of the present invention maintains the odorless state immediately after preparation without any change over time. I was This means that the purple corn pigment produced by the method of the present invention not only contains no or almost no odor component exhibiting an odor, but also a foreign substance which is a precursor of the odor component. Is not included.

Experimental example 3

(1) Preparation of purple corn pigment preparation

Assuming that fumonisin is contaminated in the raw material purple corn (female spikes (core and grain)), fumonisin is adjusted to a concentration of 5 ppm in about 16 L of purple corn pigment extract extracted according to the reference example. B1 standard was added and used as the starting material for the preparation of the purple corn pigment preparation. In the subsequent operation, the purple corn pigment extract was purified according to the preparation method of the product of the present invention and the comparative product described in Experimental Example 2 above, and a purple corn pigment preparation having a color value of E ^{1 G%} _lcm = 60 was obtained 793 g. (Product of the present invention) and 823 g (comparative product) of a purple corn pigment preparation having a color value of E ^{1 G%} _lcm = 60 were prepared.

(2) Determination of kapi venom (fumonisin)

Next, the content of the mold venom (fumonisin) in the purple corn pigment preparations (the present invention product and the comparative product) prepared above was quantitatively analyzed using liquid chromatography (HPLC). In addition, the preparation of the analysis test sample and the conditions of the HPLC analysis were in accordance with the method of Experimental Example 1.

The analysis results (chromatogram) of the analysis test sample obtained from the comparative product are shown in Fig. 2A, and the analysis results (chromatogram) of the analysis test sample obtained from the product of the present invention are shown in Fig. 2B. As can be seen from Fig. 2A, the comparative purple corn pigment preparation detected 2.96 ppm of fumonisin B1 per E1 ^Q% _cm = 60, whereas the purple corn pigment of the present invention For pigment preparations, Monisin was not detected. For this reason, according to the method for preparing purple corn pigment (purification method) of the present invention, even if mold is generated in purple corn used as a raw material, fumonisin which is a toxic component thereof is removed. Therefore, it can be seen that a safe pigment preparation of purple corn pigment can be provided.

Further, as shown in the results of Experimental Example 1, Experimental Example 3 and Experimental Example 2, according to the preparation method of the present invention, the fungus venom fumonisin is significantly removed, and the odor causing odor is also reduced. It can be seen that since the components and the contaminants as precursors thereof are significantly removed, it is possible to obtain a safe, odorless or slightly odorous purple corn pigment preparation. That is, the method of the present invention can be used as a method for removing fumonisin and odor-causing odor components and its precursors. It is useful as a method for producing pigments, and also as a method for highly purifying purple corn pigment.

Example 1 Preparation of purple corn pigment preparation

Approximately 16 L of purple corn pigment extract prepared according to the method of Reference Example was adsorbed to 1.5 L of resin (styrene vinyl benzene copolymer: Diamond HP20, manufactured by Mitsubishi Chemical Corporation) under the conditions of SV = 1 and a temperature of 20 ° C. The resin was passed, and the resin was washed with 5 L of water (SV = 1). Next, 3 L of a 30 v / v% aqueous ethanol solution was passed through the obtained resin (SV = 1, temperature: 20), and the desorbed liquid was recovered.

The eluate was treated with an ultrafiltration membrane (AHP-2013 membrane: manufactured by Asahi Kasei Corporation, molecular weight cut off: 50,000) at 3 kg / cm ² at 20 ° C. to obtain an ultrafiltration permeate. Next, sulfuric acid was added to the obtained ultrafiltration permeate to adjust the pH to 2.0, and 5 L of water was further added thereto to perform reverse osmosis membrane treatment (NTR-7250 membrane: manufactured by Nitto Denko; , 000) to obtain 1 L of reverse osmosis membrane treatment solution. At this time, the contaminants were permeated and removed as a filtrate, and the purified dye component was concentrated as a residual liquid. This reverse osmosis treatment solution was then concentrated under reduced pressure to obtain 80 g of a significantly purified dye solution having a color value of E ^{1 G%} _lcm = 200. This pigment solution contains 3.1% by weight of cyanidin 3-0-] 3-D-glucoside, which is the main pigment component of purple corn pigment. Was. 130 g of water, 40 g of ethyl alcohol and 10 g of citrate (crystal) were added to 80 g of this dye solution to prepare 260 g of a purple corn dye preparation having a color value of E ^{1 D%} i _cm = 60 (the present invention). ). The pigment preparation was odorless. Industrial applicability

The purple corn pigment of the present invention is highly purified, so that the purple corn used as a raw material, in particular, a toxic component of humic acid (fumonisin) that may be generated in the spikelets (core or grain) of the corn. ) Is a safe, odorless or slightly odorous pigment in which the odor derived from the aroma components and foreign substances contained in the purple corn female ears (core or berries) has been removed or significantly reduced. It is. Further, the purple corn pigment of the present invention is one in which a change over time such as an odor return phenomenon is significantly suppressed by the influence of light or heat during long-term storage. Therefore, the pigment of the present invention or the pigment preparation containing the pigment can be used safely and without odor problem for coloring beverages and other foods, pharmaceuticals, quasi-drugs, cosmetics, and the like.

Further, according to the method for preparing purple corn pigment of the present invention, even if mold (for example, F-paint rium momliforme or F. proliferatum) is generated in the purple corn used as a raw material, the Since the component (fumonicin) can be significantly removed, a safe purple corn pigment and a pigment preparation can be provided. Therefore, the method for preparing purple corn pigment of the present invention is useful as a safe method for preparing purple corn pigment.

Claims

The scope of the claims

1. Pass the purple corn pigment extract through the adsorbent resin, wash the resin with the adsorbed pigment with water, and then use a 25-45 v / v% alcohol aqueous solution as the desorbent to remove the resin from the resin. A method for preparing a purple corn pigment, comprising a step of removing a purple corn pigment.

2. The method for preparing a purple corn pigment according to claim 1, wherein the purple corn pigment extract is acidic water or an acidic aqueous solution containing 20 v / v% or less of alcohol.

3. The resin according to claim 1, wherein a desorbent having a volume of 1.5 to 2.5 times the resin volume is passed through the resin at a velocity of SV (space velocity) = 0.8 to 1.5 after washing with water. For preparing a purple corn pigment.

4. The method for preparing a purple corn dye according to claim 1, wherein the adsorption resin is a crosslinked styrene-based porous polymer.

5. Passing the purple corn pigment extract through the adsorption resin, washing with water, and desorbing the purple corn pigment from the resin using a 25 to 45 Wv% alcohol aqueous solution as a desorbing solution 3. The method for preparing a purple corn pigment according to claim 1, wherein the method comprises a step of removing fumonisin.

6. At least one treatment selected from the group consisting of adsorption treatment, ion exchange treatment, acid treatment, extraction treatment and membrane separation treatment is applied to the adsorption treatment liquid obtained in the step described in claim 1. A method for preparing a purple corn pigment.

7. The method for preparing a purple corn pigment according to claim 6, wherein a membrane separation treatment is performed after the treatment step described in claim 1.

8. The method for preparing a purple corn pigment according to claim 6, wherein the membrane separation treatment is at least one of a reverse osmosis membrane treatment and an ultrafiltration membrane treatment.

9. The method for preparing a purple corn dye according to claim 7, wherein an acid treatment is performed before the membrane separation treatment.

10. The purple light according to claim 9, wherein the acid treatment is performed under high temperature conditions. 方法 Method of preparing sorghum pigment.

11. A purple corn pigment that does not contain fumonisin prepared by the method of claim 1.

12. A purple corn pigment prepared by the method according to claim 1, which has a color value of 12.

E ^10% _lcm = 60

13. The fragrance component in the purple corn pigment is at least one selected from the group consisting of acetic acid, getyl malonate, 4-pinyl-2-methoxyphenol and 4-vinylphenol. Purple corn pigment.

14. A purple corn pigment prepared by the method according to claim 1, which has a color value of 14.

E ^10% _lcm = 60

A purple corn pigment having a total concentration of acetic acid, malonic acid getyl ester, 4-vinyl-2-methoxyphenol and / or 4-vinylphenol that is 20 ppm or less.

15. A pigment preparation containing the purple corn pigment according to claim 11.